CN115090327A - Covalent organic framework photocatalytic material with controllable coordination site number and loaded metal monoatomic atom, and preparation method and application thereof - Google Patents
Covalent organic framework photocatalytic material with controllable coordination site number and loaded metal monoatomic atom, and preparation method and application thereof Download PDFInfo
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- CN115090327A CN115090327A CN202210658390.6A CN202210658390A CN115090327A CN 115090327 A CN115090327 A CN 115090327A CN 202210658390 A CN202210658390 A CN 202210658390A CN 115090327 A CN115090327 A CN 115090327A
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- organic framework
- small
- covalent organic
- reaction
- photocatalytic material
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000011068 loading method Methods 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 150000003384 small molecules Chemical class 0.000 claims description 38
- 239000002243 precursor Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- SUQGULAGAKSTIB-UHFFFAOYSA-N 6-(5-formylpyridin-2-yl)pyridine-3-carbaldehyde Chemical compound N1=CC(C=O)=CC=C1C1=CC=C(C=O)C=N1 SUQGULAGAKSTIB-UHFFFAOYSA-N 0.000 claims description 14
- 239000011941 photocatalyst Substances 0.000 claims description 14
- ALXPZLQBSUZCHN-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-dicarbaldehyde Chemical compound C1=CC(C=O)(C=O)CC=C1C1=CC=CC=C1 ALXPZLQBSUZCHN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 6
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- GVWYIGSUECJNRM-UHFFFAOYSA-N pyridine-2,5-dicarbaldehyde Chemical compound O=CC1=CC=C(C=O)N=C1 GVWYIGSUECJNRM-UHFFFAOYSA-N 0.000 claims description 5
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical group O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- UNMGLSGVXHBBPH-BVHINDLDSA-L nickel(2+) (NE)-N-[(3E)-3-oxidoiminobutan-2-ylidene]hydroxylamine Chemical compound [Ni++].C\C(=N/O)\C(\C)=N\[O-].C\C(=N/O)\C(\C)=N\[O-] UNMGLSGVXHBBPH-BVHINDLDSA-L 0.000 claims description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 150000004677 hydrates Chemical class 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000005859 coupling reaction Methods 0.000 description 26
- HQSCPPCMBMFJJN-UHFFFAOYSA-N 4-bromobenzonitrile Chemical compound BrC1=CC=C(C#N)C=C1 HQSCPPCMBMFJJN-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- XDJAAZYHCCRJOK-UHFFFAOYSA-N 4-methoxybenzonitrile Chemical compound COC1=CC=C(C#N)C=C1 XDJAAZYHCCRJOK-UHFFFAOYSA-N 0.000 description 8
- 150000001491 aromatic compounds Chemical class 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000013032 photocatalytic reaction Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- 150000007530 organic bases Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- -1 s-triphenylamine Chemical compound 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- JYAQYXOVOHJRCS-UHFFFAOYSA-N 1-(3-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Br)=C1 JYAQYXOVOHJRCS-UHFFFAOYSA-N 0.000 description 1
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- XLQSXGGDTHANLN-UHFFFAOYSA-N 1-bromo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Br)C=C1 XLQSXGGDTHANLN-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- DMSHUVBQFSNBBL-UHFFFAOYSA-N 5-bromopyridine-2-carbonitrile Chemical compound BrC1=CC=C(C#N)N=C1 DMSHUVBQFSNBBL-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- XZIAFENWXIQIKR-UHFFFAOYSA-N ethyl 4-bromobenzoate Chemical compound CCOC(=O)C1=CC=C(Br)C=C1 XZIAFENWXIQIKR-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- CZNGTXVOZOWWKM-UHFFFAOYSA-N methyl 4-bromobenzoate Chemical compound COC(=O)C1=CC=C(Br)C=C1 CZNGTXVOZOWWKM-UHFFFAOYSA-N 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a covalent organic framework photocatalytic material with controllable coordination site number and single metal atom loading, and a preparation method and application thereof. The photocatalytic material of the present invention comprises a covalent organic framework and a metal; the covalent organic framework has a lamellar structure, and the metal is loaded on the surface and/or in the pores of the covalent organic framework in the form of ions; the covalent organic framework includes coordination sites that control the loading of metal in an amount of 0.001 to 10 wt%. The photocatalytic material can be used for constructing a catalyst system and is applied to aromatic hydrocarbon-oxygen cross coupling reaction.
Description
Technical Field
The invention relates to the field of synthesis of metal monatomic catalysts, in particular to a covalent organic framework photocatalytic material with controllable coordination site number and loaded with metal atoms, and a preparation method and application thereof.
Background
Monatomic catalysts have a unique electronic structure and often are accompanied by an unsaturated coordination environment. Compared with metal nanoparticles or metal clusters, the monatomic metal catalyst can expose more catalytic sites and has more excellent atom utilization. In recent years, more and more monatomic catalysts are developed as photocatalysts to perform photocatalytic reactions, but the interaction between the monatomic catalytic center and the photocatalyst is limited by various factors, such as material quantum yield, bulk diffusion, interfacial interactions, electron or energy transfer, and the like. The covalent organic framework has the advantages of adjustable structure, easy modification and the like, can control the aperture size of the substrate material, and can controllably change the coordination environment of the single metal atom, thereby solving the problems by optimizing the substrate of the metal single atom catalyst.
Disclosure of Invention
The invention provides a photocatalytic material comprising a covalent organic framework and a monoatomic metal bonded by a coordination bond; the covalent organic framework has a lamellar structure, and the monoatomic metal is loaded on the surface and/or in pores of the covalent organic framework in the form of ions; the covalent organic framework includes coordination sites that can control the loading of the monoatomic metal by from 0.001 to 10 weight percent, such as from 0.2 to 4.6 weight percent.
According to an embodiment of the invention, the covalent organic framework has a light absorbing capacity.
According to an embodiment of the invention, the covalent organic framework is formed by a group A small molecule precursor, B 1 Small like molecule and B 2 And (3) small molecule-like reaction.
Preferably, the A-type small molecule precursor is selected from at least one of 1,3, 5-tri (4-aminophenyl) benzene, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, triphenylamine and melamine.
Preferably, B is 1 The small-like molecule is selected from one of terephthalaldehyde and 4, 4-biphenyldicarboxaldehyde.
Preferably, B is 2 The small molecule is selected from one of pyridine-2, 5-dicarboxaldehyde and 2,2 '-bipyridine-5, 5' -dicarboxaldehyde.
Preferably, the A-type small molecule precursor and the B-type small molecule precursor 1 Class of small molecules and said B 2 The molar ratio of the sum of the small-like molecules is 2 (0.1-5), for example 2: 3.
Further, B is 1 Class small molecule and B 2 The molar ratio of the small molecule-like is 1:1-99:1, such as 1:1, 4:1, 9:1, 24:1, 99: 1.
According to an embodiment of the invention, the covalent organic framework comprises a recurring structural unit of formula i below, said structural unit of formula i constituting a cyclic structure by repeated linkage:
wherein,
and
through imino linkage;
represents R 1 ，
Represents R 2 And/or R 3 ,.. shows repetition and extension of the structure.
Preferably, each of the ring structures formed includes
And
at least 6 and 6 or more of each of them are bonded by imine bond, preferably
And
each 6 are linked by imine bonds.
According to an embodiment of the invention, in said covalent organic framework, said R 2 And R 3 In a molar ratio of 1:1 to 99:1, for example 1:1, 4:1, 9:1, 24:1, 99: 1.
Preferably, said R is 1 Is provided by the A-type small molecule precursor.
Preferably, said R is 2 From said B 1 Provided by a small-like molecule.
Preferably, said R is 3 From said B 2 Provided by a small-like molecule.
According to a preferred embodiment of the invention, the covalent organic framework comprises a cyclic structural unit represented by formula II below:
according to an embodiment of the invention, in the cyclic structural unit of formula II, R 1 At least one member selected from the following structural units:
According to an embodiment of the invention, in the cyclic structural unit of formula II, R 2 Is selected from
Wherein represents the site forming the imine bond.
According to an embodiment of the invention, in the cyclic structural unit of formula II, R 3 Is selected from
Wherein denotes the site forming the imine bond.
According to an exemplary aspect of the present invention, the photocatalytic material includes a covalent organic framework and Ni metal, the Ni metal being connected in coordination bonds; the Ni metal is loaded on the surface and/or in the pores of the semiconductor in the form of ions, and the loading amount of the Ni metal is 0.001-10 wt%, preferably 0.2-4.6 wt%.
Preferably, the covalent organic framework is prepared from the following raw materials:
the A-type micromolecule precursor is 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine;
B 1 the small-like molecules are 4, 4-biphenyldicarboxaldehyde and B 2 Micromolecular 2,2 '-bipyridine-5, 5' -dicarboxaldehyde; wherein, B 1 Class small molecule and B 2 The molar ratio of the small molecules is 1:1, 4:1, 9:1, 24:1 and 99: 1.
Further, the A-type small molecule precursor and the B 1 Small like molecule and B 2 The molar ratio of the sum of the small molecules is 2: 3.
Preferably, the covalent organic framework comprises a cyclic structural unit of formula II, wherein R 1 Is selected from
R 2 Is selected from
R 3 Is selected from
The R is 2 And R 3 In a molar ratio of 1:1, 4:1, 9:1, 24:1 or 99: 1.
The invention also provides a preparation method of the photocatalytic material, which comprises the following steps:
(1) the A-type small molecule precursor and B 1 Class small molecule, B 2 Reacting the small-like molecules in a certain atmosphere to obtain a covalent organic framework as a substrate;
(2) and (2) dispersing the substrate in the step (1) in an organic solvent containing metal salt, and reacting to obtain the photocatalytic material.
According to an embodiment of the present invention, in step (1), the group a small molecule precursor has the meaning as described above, and may be at least one selected from 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, s-triphenylamine, and melamine, for example, one, two, or more.
According to an embodiment of the invention, in step (1), said B 1 The small molecular is selected from terephthalaldehyde and 4, 4-biphenyldicarboxaldehyde.
According to an embodiment of the present invention, in step (1), said B 2 The small molecule is selected from one of pyridine-2, 5-dicarboxaldehyde and 2,2 '-bipyridine-5, 5' -dicarboxaldehyde.
According to an embodiment of the invention, B 1 Small like molecules and B 2 The molar ratio of the small molecule-like is 1:1-99:1, such as 1:1, 4:1, 9:1, 24:1, 99: 1.
According to an exemplary embodiment of the present invention, the group a small molecule precursor is 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine; b is described 1 The micromolecule is 4, 4-biphenyldicarboxaldehyde; b is described 2 The micromolecule is 2,2 '-bipyridine-5, 5' -dicarboxaldehyde; wherein, the A-type small molecule precursor and the B 1 Small like molecule and B 2 The molar ratio of the sum of the small-like molecules is 2: 3; b is 1 Class of small molecules with B 2 The molar ratio of the small molecules is 1:1, 4:1, 9:1, 24:1 and 99: 1.
According to an embodiment of the present invention, in the step (1), the reaction is carried out in a reaction solvent and a reaction catalyst.
Preferably, the reaction solvent is at least one, two or more selected from toluene, mesitylene, ortho-dichlorobenzene, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and dioxane, preferably mesitylene and dioxane.
According to an embodiment of the present invention, the reaction catalyst is selected from one of formic acid and acetic acid, preferably acetic acid.
According to the embodiment of the present invention, in step (1), the mass-to-volume ratio of the group a small molecule precursor to the reaction solvent is not particularly limited, and may be selected from those known in the art, for example, 184mg:12 mL.
According to an embodiment of the present invention, in the step (1), the volume ratio of the reaction catalyst and the reaction solvent is not particularly limited, and may be selected from those known in the art, for example, 0.4: 12.
According to an embodiment of the present invention, in step (1), the mass-to-volume ratio of the group a small molecule precursor to the reaction catalyst is not particularly limited, and is, for example, 184mg:0.4 mL.
According to an embodiment of the invention, the atmosphere of step (1) is selected from inert atmospheres, for example an argon atmosphere.
According to an embodiment of the present invention, the atmosphere in step (1) may be changed by a method known in the art, for example, a bubbling method or a low-temperature vacuum degassing method.
According to an embodiment of the present invention, in step (1), the temperature of the reaction may be 10 to 180 ℃, for example 25 ℃.
According to an embodiment of the present invention, in step (1), the reaction time may be 6 to 168 hours, for example 72 hours.
According to an embodiment of the invention, in step (1), the reaction may optionally be stirred or unstirred.
According to an embodiment of the present invention, in step (1), after the reaction, further washing and/or drying may be performed.
Preferably, the washing can be carried out with an organic solvent, for example a self-polar solvent. Further, the organic solvent may be one, two or more selected from methanol, ethanol, isopropanol, acetic acid (glacial acetic acid), dichloromethane, acetonitrile, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide.
Preferably, the number of washing times of each organic solvent is at least two.
Illustratively, the washing is carried out with any two of the organic solvents described above, each solvent being washed at least twice.
Preferably, the drying time is 2-24h, for example 12 h.
Preferably, the temperature of the drying is 40-180 ℃, for example 60 ℃.
According to an embodiment of the present invention, in the step (2), the metal salt may be selected from nickel salts.
Preferably, the nickel salt is, for example, at least one selected from nickel bromide, nickel chloride, nickel nitrate, nickel sulfate, nickel dimethylglyoxime, nickel titanyl cyanine tetrasulfonic acid tetrasodium salt, or a hydrate of each thereof.
According to an embodiment of the invention, in step (2), the organic solvent has the meaning as described above.
According to an embodiment of the present invention, in the step (2), the mass ratio of the metal salt to the substrate may be (1-100):50, for example (20-60): 50.
According to an embodiment of the invention, in step (2), the concentration of the metal salt in the polar organic solvent may be in the range of 1-20mmol/L, for example 10mmol/L, exemplarily 7.71 mmol/L.
According to an embodiment of the present invention, in the step (2), the reaction conditions include: the temperature of the reaction may be 10-120 ℃, e.g. 25 ℃; the reaction time may be 6-168h, for example 72 h.
According to an embodiment of the present invention, in the step (2), after the reaction, further washing and/or drying may be performed.
Preferably, the washing and drying have the meaning as described above.
The invention also provides the application of the photocatalytic material as a photocatalyst.
The invention also provides a photocatalyst which comprises the photocatalytic material.
The invention also provides the application of the photocatalyst in aromatic hydrocarbon-oxygen cross coupling reaction, such as the application in catalyzing the reaction of preparing ether or phenol from halogenated hydrocarbon and alcohol or water.
According to an embodiment of the present invention, the halogenated hydrocarbon may be a halogenated aromatic compound, for example, at least one selected from the group consisting of p-bromoacetophenone, p-bromotrifluorotoluene, p-bromobenzonitrile, p-bromobenzaldehyde, ethyl p-bromobenzoate, methyl p-bromobenzoate, m-bromoacetophenone, 4-bromobenzophenone, 5-bromo-2-cyanopyridine.
According to an embodiment of the present invention, the alcohol may be a liquid alcohol, for example, at least one selected from methanol, ethanol, isopropanol, n-propanol, n-butanol.
According to an embodiment of the present invention, the catalytic halogenated hydrocarbon and alcohol or water to ether or phenol reaction comprises the steps of: and under the illumination condition, carrying out photocatalytic reaction on the photocatalyst, the halogenated aromatic compound, the organic base, the alcohol or the water to obtain a product.
According to an embodiment of the present invention, the photocatalytic reaction may be performed in a photoreactor.
Preferably, the photoreactor is a light-transmitting reactor, such as a quartz glass tube reactor; further preferably, the photocatalytic reactor is sealed to remove oxygen.
According to an embodiment of the present invention, the light irradiation condition is preferably light irradiation of more than 400nm, for example, 420nm light irradiation.
According to an embodiment of the present invention, the organic base may be selected from at least one of quinuclidine, triethylamine, trimethylamine, N-diisopropylethylamine, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1, 4-diazabicyclo [2.2.2] octane.
According to an embodiment of the present invention, the concentration of the photocatalyst in the reaction system is 0.1 to 10g/L, preferably 0.5 g/L.
According to an embodiment of the present invention, the concentration of the halogenated aromatic compound in the reaction system is 0.002 to 1mol/L, preferably 0.01 mol/L.
According to an embodiment of the present invention, the mass ratio of the photocatalyst to the halogenated aromatic compound is (1-10): (100-200), for example, 5: 182.
According to an embodiment of the invention, the molar volume ratio of the halogenated aromatic compound to the alcohol may be 1mmol (0.5-20) ml, such as 1mmol (1-10) ml, illustratively 1mmol:10 ml.
According to embodiments of the present invention, the molar ratio of the halogenated aromatic compound to the organic base may be 1 (0.5-20), such as 1 (1-10), illustratively 1: 2.
According to an embodiment of the invention, the conditions of the photocatalytic reaction further comprise: the reaction temperature may be from 10 to 80 ℃, e.g. 25 ℃; the irradiation time may be 0.5h or more, examples 1h, 2h, 6h, 8h, and 12 h.
According to an embodiment of the present invention, the photocatalytic reaction may also be performed under stirring.
Advantageous effects
The number of coordination sites of the covalent organic framework is adjusted to change the load capacity of the monatomic metal, so that the photocatalytic material is obtained, wherein the covalent organic framework is connected with the metal through a chemical bond, so that the electron transfer between the covalent organic framework and the metal is promoted, and the activation of the covalent organic framework as a photocatalyst is further improved; the optimal metal loading is obtained by adjusting the concentration of the coordination sites of the substrate, and when the metal loading is used for visible light catalytic reaction, the carbon-oxygen cross coupling of halogenated aromatic compounds and alcohol or water can be promoted, and ether or phenol can be obtained under the condition of high reaction substrate concentration; in addition, the photocatalyst of the present invention can be further recovered. The photocatalytic material prepared by the preparation method provided by the invention usually adopts organic base (such as DIPEA) with lower cost, and compared with quinuclidine organic base commonly used in the prior art, the preparation method provided by the invention has the advantage that the preparation cost is greatly reduced on the premise of basically same dosage (namely the molar ratio of the substrate to the organic base is 1: 2).
Drawings
The catalysts numbered 1-5 in fig. 1a correspond to the photocatalysts prepared in examples 1-5 with different loading due to site number modulation, respectively.
Numbers 1-5 in FIG. 1b correspond to the IR spectra of the covalent organic frameworks prepared in examples 1-5, respectively.
FIG. 2a is a schematic view of the structure of the organic framework of embodiment 1.
FIG. 2b is a high resolution TEM image of the photocatalyst prepared in example 1.
FIG. 3 is a reactant/product gas spectrum of the coupling reaction of p-bromobenzonitrile with methanol in application example 1.
FIG. 4 is a reaction/product gas spectrum of the coupling reaction of p-bromobenzonitrile and methanol in application example 2.
FIG. 5 is a reactant/product gas spectrum of the coupling reaction of p-bromobenzonitrile with methanol in application example 3.
FIG. 6 is a reactant/product gas spectrum of the coupling reaction of p-bromobenzonitrile with methanol in application example 4.
FIG. 7 is a reaction/product gas spectrum of the coupling reaction of p-bromobenzonitrile with methanol in application example 5.
FIG. 8 is a nuclear magnetic diagram of the product of the coupling reaction of p-bromobenzonitrile and methanol in application example 1.
FIG. 9 is a reactant/product gas spectrum of a coupling reaction of p-bromobenzonitrile with methanol in comparative application example 1.
FIG. 10 is a reaction/product gas spectrum of the coupling reaction of p-bromobenzonitrile with methanol in comparative application example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The preparation method of the photocatalytic material comprises the following steps:
(1) 184mg of 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine as a precursor of the A-type micromolecule and 162.17mg of B 1 Micromolecular 4, 4-biphenyldicarboxaldehyde and 1.65mg B 2 Micromolecular 2,2 '-bipyridine-5, 5' -dicarboxaldehyde, 10.2mL mesitylene and 1.8mL dioxane serving as reaction solvents, 0.4mL glacial acetic acid and magnetons are added. Connecting the pressure-resistant pipe to the double-row pipe, and replacing argon into the reaction pipe for three times by using a method of liquid nitrogen cooling, air extraction, gas replacement and normal temperature recovery. Stirring at normal temperature for reaction for 72h, filtering with a mobile phase filtering device, washing with N, N-dimethylacetamide and ethanol for three times respectively to obtain a bright yellow solid which is the substrate of the covalent organic framework, and drying for 12h for later use. The infrared analysis and characterization result shows that 1698cm is obtained -1 The C ═ N characteristic absorption peak at (a) demonstrates the successful synthesis of the material, as shown at 1 in fig. 1 b.
(2) And (2) adding 55mg of nickel chloride hexahydrate and 30ml of ethanol into 50mg of the substrate dried in the step (1), stirring and reacting for 12 hours to obtain a bright yellow solid, washing the bright yellow solid with N, N-dimethylacetamide and ethanol for three times, and drying the bright yellow solid (the drying condition is vacuum drying for 12 hours at 60 ℃) to obtain the photocatalytic material, wherein the mark is 1:99 COF-Ni. ICP-OES tests showed that the loading of Ni metal in the photocatalytic material in this example was 0.20 wt.%, and as shown in 1 of fig. 1a, the photocatalytic material prepared in this example was pale yellow.
The schematic structure of the covalent organic framework is shown in FIG. 2aWherein repetition and epitaxy of the structure are indicated; specifically, the covalent organic framework comprises a cyclic structural unit shown as a formula II, wherein R is 1 Is selected from
R 2 Is selected from
R 3 Is selected from
Wherein denotes a ligation site; the R is 2 And R 3 In a molar ratio of 99: 1.
The structure of 1:99COF-Ni was determined by using a transmission electron microscope with spherical aberration correction, and as a result, as shown in FIG. 2b, it can be seen that 1:99COF-Ni has a lamellar structure, and Ni is uniformly distributed on the surface and/or in the pores of the material in the form of single atoms.
Application example 1
The coupling reaction of aromatic hydrocarbon and alcohol includes the following steps:
5mg of 1:99COF-Ni of example 1 and 0.0182g of p-bromobenzonitrile, 0.035mL of N, N-diisopropylethylamine were added to 10mL of methanol as a reaction mixture, then the reaction mixture was purged with argon under magnetic stirring for at least 15 minutes to remove oxygen, and photocatalytic reaction was performed using LED light irradiation at a wavelength of 420nm to obtain product 1.
FIG. 3 is a product gas spectrum of the coupling reaction of p-bromobenzonitrile with methanol in application example 1. After 2 hours of irradiation, the conversion rate of the product 1 is 75.9 percent, the product 1 is p-methoxy benzonitrile, and the selectivity is 99.9 percent; after 5h of irradiation, the conversion of the product 1 is 98.5%, the product 1 is p-methoxybenzonitrile, and the selectivity is 99.9%.
FIG. 8 is a nuclear magnetic diagram of the product of the methanol coupling reaction of p-bromobenzonitrile in application example 1. As can be seen from FIGS. 3 and 8, after 5h, the reaction is completed, the product is single, and the product produced by the reaction is p-methoxyphenylnitrile.
Example 2
Preparation method of photocatalytic material referring to example 1, except that: in the step (1), the amounts of 4, 4-biphenyldicarboxaldehyde and 2,2 '-bipyridine-5, 5' -dicarboxaldehyde used were 157.26mg and 6.61mg, respectively. The photocatalytic material was obtained and was reported as 1:24 COF-Ni.
Infrared 1698cm, as shown at 2 in fig. 1b -1 The C ═ N characteristic absorption peak at (a) demonstrates the successful synthesis of the material.
The loading of Ni in the photocatalytic material of this example was 0.75 wt.%, and as shown in 2 of fig. 1a, the photocatalytic material prepared in this example was yellow.
The covalent organic framework in this example is essentially the same as in example 1, wherein R is 2 And R 3 In a molar ratio of 1: 24.
Application example 2
The coupling reaction of aromatic hydrocarbon with alcohol was substantially the same as in application example 1 except that the photocatalytic material 1:24COF-Ni of example 2 was used to obtain a product 2.
FIG. 4 is a gas spectrum of product 2 of the coupling reaction of p-bromobenzonitrile with methanol in application example 2. After 2 hours of irradiation, the conversion rate of the product 2 is 91.1 percent, the product 2 is p-methoxy benzonitrile, and the selectivity is 98.4 percent; after 5h of irradiation, the conversion of the product 2 is 100%, the product 2 is p-methoxybenzonitrile, and the selectivity is 99.9%.
Example 3
Preparation method of photocatalytic material referring to example 1, except that: in the step (1), the dosages of the 4, 4-biphenyldicarboxaldehyde and the 2,2 '-bipyridine-5, 5' -dicarboxaldehyde are 147.43mg and 16.54mg respectively. The photocatalytic material was obtained and was reported as 1:9 COF-Ni.
Infrared 1698cm, as shown at 3 in fig. 1b -1 The characteristic absorption peak of C-N proves the successful synthesis of the material.
The loading of Ni in the photocatalytic material of this example was 1.6 wt.%, and as shown in fig. 1a, at 3, the photocatalytic material prepared in this example was yellow.
The covalent organic framework in this example is essentially the same as in example 1, wherein R is 2 And R 3 In a molar ratio of 1: 9.
Application example 3
The coupling reaction of aromatic hydrocarbon with alcohol was substantially the same as in application example 1 except that the photocatalytic material 1:9COF-Ni of example 3 was used to obtain a product 3.
FIG. 5 is a gas spectrum of product 3 of the coupling reaction of p-bromobenzonitrile with methanol in application example 3. After 2 hours of irradiation, the conversion rate of the product 3 is 70.8 percent, the product 3 is p-methoxy benzonitrile, and the selectivity is 98.7 percent; after 5h of irradiation, the conversion of the product 3 was 78.6%, and the product 3 was p-methoxyphenylnitrile with a selectivity of 99.9%.
Example 4
Preparation of photocatalytic material referring to example 1, the difference is that: in the step (1), the dosages of the 4, 4-biphenyldicarboxaldehyde and the 2,2 '-bipyridine-5, 5' -dicarboxaldehyde are 109.21mg and 55.12mg respectively. Obtaining the photocatalytic material which is marked as 1:4 COF-Ni.
Infrared 1698cm, as shown at 4 in fig. 1b -1 The C ═ N characteristic absorption peak at (a) demonstrates the successful synthesis of the material.
The loading of Ni in the photocatalytic material of this example was 3.3 wt.%, and as shown in 4 of fig. 1a, the photocatalytic material prepared in this example was dark yellow.
The covalent organic framework in this example is essentially the same as in example 1, wherein R is 2 And R 3 In a molar ratio of 1: 4.
Application example 4
Coupling reaction of aromatic hydrocarbon with alcohol, substantially the same as in application example 1, except that the photocatalytic material 1:4COF-Ni of example 4 was used, product 4 was obtained.
FIG. 6 is a product 4 spectrum of the coupling reaction of p-bromobenzonitrile with methanol in application example 4. After 2 hours of irradiation, the conversion rate of the product 4 is 18.0 percent, the product 4 is p-methoxy benzonitrile, and the selectivity is 92.0 percent; after 5h of irradiation, the conversion of product 4 was 53.8% and product 4 was p-methoxyphenylnitrile with a selectivity of 90.5%.
Example 5
Preparation of photocatalytic material referring to example 1, the difference is that: in the step (1), the amounts of 4, 4-biphenyldicarboxaldehyde and 2,2 '-bipyridine-5, 5' -dicarboxaldehyde used were 82.68mg and 81.91mg, respectively. Obtaining the photocatalytic material which is marked as 1:1 COF-Ni.
As indicated by 5 in FIG. 1bInfrared 1698cm -1 The C ═ N characteristic absorption peak at (a) demonstrates the successful synthesis of the material.
As can be seen from ICP-OES tests, the loading amount of Ni metal in the photocatalytic material in this example is 4.6 wt.%, as shown in 5 in fig. 1a, the photocatalytic material prepared in this example is dark yellow.
In the photocatalytic material of this example, the covalent organic framework is essentially the same as in example 1, wherein R is as defined above 2 And R 3 In a molar ratio of 1: 1.
Application example 5
The coupling reaction of aromatic hydrocarbon with alcohol was substantially the same as in application example 1 except that the photocatalytic material 1:1COF-Ni of example 4 was used to obtain a product 5.
FIG. 7 is a gas spectrum of product 5 of the coupling reaction of p-bromobenzonitrile with methanol in application example 5. After 2 hours of irradiation, the conversion rate of the product 5 is 19.4 percent, the product 3 is p-methoxy benzonitrile, and the selectivity is 87.9 percent; after 5h of irradiation, the conversion of product 5 was 19.7% and the selectivity of product 3 was 86.1% for p-methoxyphenylnitrile.
Comparative example 1
Preparation method of photocatalytic material referring to example 1, except that: in the step (1), only 4, 4-biphenyldicarboxaldehyde was used in an amount of 163.82 mg. Obtaining the photocatalytic material which is marked as 1-COF-Ni.
It can be seen from ICP-OES tests that the loading of Ni metal in the photocatalytic material in this example is 0.03 wt.%.
In the photocatalytic material of this example, the covalent organic framework is essentially the same as in example 1, wherein R is 2 And R 3 In a molar ratio of 1:0, i.e. only R 2 Is free of R 3 。
Comparative application example 1
The coupling reaction of aromatic hydrocarbon with alcohol was substantially the same as in application example 1 except that the photocatalytic material 1-COF-Ni of comparative example 1 was used.
Fig. 9 is a gas chromatogram of a product 6 of the coupling reaction of p-bromobenzonitrile and methanol in comparative application example 1, and it can be known from a gas chromatography test that after 5 hours of light reaction, the reactant of the comparative application example is hardly converted, and the yield of the generated product, p-methoxybenzonitrile, is less than 3%.
Comparative example 2
Preparation method of photocatalytic material referring to example 1, except that: in step (1), only 2,2 '-bipyridine-5, 5' -dicarboxaldehyde was used in an amount of 165.36 mg. Obtaining the photocatalytic material, which is marked as 0-COF-Ni.
The loading amount of Ni of the photocatalytic material of the present example was 7.1 wt.%.
In the photocatalytic material of this example, the covalent organic framework is essentially the same as in example 1, wherein R is as defined above 2 And R 3 In a molar ratio of 0:1, i.e. only R 3 Is free of R 2 。
Comparative application example 2
The coupling reaction of aromatic hydrocarbon with alcohol was substantially the same as in application example 1 except that the photocatalytic material 0-COF-Ni of comparative example 2 was used.
Fig. 10 is a gas chromatogram of the coupling reaction of p-bromobenzonitrile and methanol in comparative application example 2, and it can be known from a gas chromatography test that after 5 hours of light reaction, the reactant of the comparative application example has no conversion and no product is generated.
It can be seen from this that 0-COF-Ni or 1-COF-Ni in the comparative example was used in the coupling reaction, the yield of the obtained product was only 3% at the maximum, as compared with 1:99COF-Ni of example 1; while from 1:99COF-Ni of example 1 to 1COF-Ni of example 5, with R in the photocatalytic material 3 The proportion is gradually reduced, the load of Ni is accurately regulated and controlled step by step, and the activity of the catalyst is changed regularly along with the change of the environment where the Ni is located. It can be seen that by adjusting B 1 A small molecule and B 2 The dosage ratio of the small molecules can realize the regulation and control of the site number of the photocatalytic material and the Ni load capacity, thereby directly influencing the photocatalytic activity of the coupling reaction.
In addition, when the group A small molecule precursor in examples 1-5 above is replaced with 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, sym-triphenylamine, or melamine, or B 1 The small-like molecules are replaced by terephthalaldehyde, 4-biphenyldicarboxaldehyde orB is to be 2 When the small-like molecule was replaced with pyridine-2, 5-dicarboxaldehyde or 2,2 '-bipyridine-5, 5' -dicarboxaldehyde, a photocatalytic material having the same effects as in examples 1 to 5 when used in the above-mentioned coupling reaction was obtained.
The above description is directed to exemplary embodiments of the present invention. However, the scope of protection of the present application is not limited to the above embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A photocatalytic material comprising a covalent organic framework and a monoatomic metal that is connected in coordination bonds; the covalent organic framework has a lamellar structure, and the monoatomic metal is loaded on the surface and/or in pores of the covalent organic framework in an ionic form; the covalent organic framework includes coordination sites that control the loading of the monatomic metal, which is at a loading of 0.001-10 wt%.
2. The photocatalytic material of claim 1, wherein the loading of the monoatomic metal is 0.2 to 4.6 wt%.
Preferably, the covalent organic framework has a light absorbing ability.
Preferably, the covalent organic framework is formed by a class A small molecule precursor, B 1 Small like molecule and B 2 And (3) small molecule-like reaction.
Preferably, the A-type small molecule precursor is selected from at least one of 1,3, 5-tri (4-aminophenyl) benzene, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, triphenylamine and melamine.
Preferably, B is 1 The small molecular is selected from terephthalaldehyde and 4, 4-biphenyldicarboxaldehyde.
Preferably, B is 2 The small molecule is selected from one of pyridine-2, 5-dicarboxaldehyde and 2,2 '-bipyridine-5, 5' -dicarboxaldehyde.
Preferably, said class ASmall molecule precursor, said B 1 Class of small molecules and said B 2 The molar ratio of the sum of the small-like molecules is 2 (0.1-5).
Further, B is 1 Small like molecule and B 2 The molar ratio of the micromolecules is 1:1-99: 1.
3. The photocatalytic material of claim 1 or 2, wherein the covalent organic framework comprises a repeating structural unit represented by formula i below, wherein the structural unit represented by formula i below forms a cyclic structure through repeated connection:
wherein,
and
through imino linkage;
represents R 1 ，
Represents R 2 And/or R 3 ,.. shows repetition and extension of the structure.
Preferably, each of the ring structures formed includes
And
at least 6 and 6 or more of each of them are connected by imine bond, preferably
And
each 6 are linked by imine bonds.
Preferably, in said covalent organic framework, said R 2 And R 3 In a molar ratio of 1:1 to 99: 1.
Preferably, said R is 1 Is provided by the A-type small molecule precursor.
Preferably, said R is 2 From said B 1 Provided by a small-like molecule.
Preferably, said R is 3 From said B 2 Provided by a small-like molecule.
4. A photocatalytic material as in any of claims 1-3, characterized by that, the covalent organic framework comprises a cyclic structural unit as shown in formula ii below:
preferably, in the cyclic structural unit represented by the formula II, R 1 At least one member selected from the following structural units:
Preferably, in the cyclic structural unit represented by the formula II, R 2 Is selected from
Wherein denotes the site forming the imine bond.
Preferably, in the cyclic structural unit represented by the formula II,R 3 is selected from
Wherein represents the site forming the imine bond.
Preferably, the photocatalytic material comprises a covalent organic framework and Ni metal, the Ni metal being connected in coordination bonds; the Ni metal is loaded on the surface and/or in the pores of the semiconductor in the form of ions, and the loading amount of the Ni metal is 0.001-10 wt%, preferably 0.2-4.6 wt%; preferably, the covalent organic framework is prepared from the following raw materials:
the A-type micromolecule precursor is 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine;
B 1 the small-like molecules are 4, 4-biphenyldicarboxaldehyde and B 2 Micromolecular 2,2 '-bipyridine-5, 5' -dicarboxaldehyde; wherein, B 1 Class small molecule and B 2 The molar ratio of the small molecules is 1:1, 4:1, 9:1, 24:1 and 99: 1.
Further, the A-type small molecule precursor and the B 1 Small like molecule and B 2 The molar ratio of the sum of the small-like molecules is 2: 3.
5. The method for preparing a photocatalytic material according to any one of claims 1 to 4, characterized by comprising the steps of:
(1) the A-type small molecule precursor and B 1 Class small molecule, B 2 Reacting the small-like molecules in a certain atmosphere to obtain a covalent organic framework as a substrate;
(2) and (2) dispersing the substrate in the step (1) in an organic solvent containing metal salt, and reacting to obtain the photocatalytic material.
6. The preparation method according to claim 5, wherein in step (1), the group A small molecule precursor is at least one selected from the group consisting of 1,3, 5-tris (4-aminophenyl) benzene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, sym-triphenylamine and melamine.
Preferably, in step (1), said B 1 The small molecular is selected from terephthalaldehyde and 4, 4-biphenyldicarboxaldehyde.
Preferably, in step (1), said B 2 The small molecule is selected from one of pyridine-2, 5-dicarboxaldehyde and 2,2 '-bipyridine-5, 5' -dicarboxaldehyde.
Preferably, B is 1 Class of small molecules with B 2 The molar ratio of the micromolecules is 1:1-99: 1.
7. The production method according to claim 5 or 6, characterized in that, in the step (1), the reaction is carried out in a reaction solvent and a reaction catalyst.
Preferably, the reaction solvent is at least one, two or more selected from toluene, mesitylene, ortho-dichlorobenzene, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and dioxane, preferably mesitylene and dioxane.
Preferably, the reaction catalyst is selected from one of formic acid and acetic acid, and is preferably acetic acid.
Preferably, the atmosphere of step (1) is selected from inert atmospheres.
Preferably, in step (1), the temperature of the reaction is 10-180 ℃.
Preferably, in the step (1), the reaction time is 6-168 h.
Preferably, in step (1), after the reaction, further washing and/or drying is performed.
8. The production method according to any one of claims 5 to 7, wherein in the step (2), the metal salt is selected from nickel salts.
Preferably, the nickel salt is selected from at least one of nickel bromide, nickel chloride, nickel nitrate, nickel sulfate, nickel dimethylglyoxime, nickel titanyl cyanine tetrasulfonic acid tetrasodium salt, or their respective hydrates.
Preferably, in the step (2), the mass ratio of the metal salt to the substrate is (1-100): 50.
Preferably, in the step (2), the concentration of the metal salt in the polar organic solvent is 1 to 20 mmol/L.
Preferably, in step (2), the reaction conditions include: the reaction temperature is 10-120 ℃; the reaction time is 6-168 h.
Preferably, in step (2), after the reaction, further washing and/or drying is performed.
9. A photocatalyst, characterized in that it comprises the photocatalytic material according to any one of claims 1 to 4.
10. Use of a photocatalyst according to claim 9 in aromatic-oxygen cross-coupling reactions, for example in reactions catalysing the preparation of ethers or phenols from halogenated hydrocarbons and alcohols or water.
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| CN116273188A (en) * | 2023-03-01 | 2023-06-23 | 岭南师范学院 | Application of porous organic framework material loaded with metal in catalyzing Pictet-Spengler reaction |
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| CN108435255A (en) * | 2018-04-09 | 2018-08-24 | 陕西理工大学 | A kind of monatomic catalyst of iridium and the preparation method and application thereof |
| CN112156758A (en) * | 2020-09-15 | 2021-01-01 | 清华大学 | Porous material and preparation method and application thereof |
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